The projection technique of Sanchez-Portal *et al.*
[48] have been implemented. The eigenstates
obtained from PW calculations when
sampling at a given wavevector are projected onto Bloch
functions formed from a localised basis set . In this case, the natural choice of basis set is the set of
atomic pseudo-orbitals generated from the pseudopotentials used in the
calculation. However, care must be taken when performing the
projection because this basis set is neither orthonormal nor complete.

The overlap matrix of the localised basis set, , is defined :

These overlaps are computed in reciprocal space, as the imposition of periodic boundary conditions implies that the orbitals need only be evaluated on a discrete reciprocal space grid. The overlaps between orbitals on different atomic sites can be calculated on the same grid with the application of a phase factor. The representations of the atomic pseudo-orbitals on the discrete reciprocal space grid may be calculated by Fourier transformation of the real space wavefunctions generated during construction of the pseudopotentials, or can be generated using the CASTEP code.

The overlaps between the plane wave states and the basis functions,

are also calculated in reciprocal space, as this is the natural representation of the plane wave states.

The quality of the projection may be assessed by the calculation of a spilling parameter,

where is the number of PW eigenstates, are the weights associated with the calculated points in the Brillouin zone and is the projection operator of Bloch functions with wave vector generated by the atomic basis.

where are the duals of the atomic basis states such that

The spilling parameter varies between one, in the case that the atomic
basis set is orthogonal to the PW eigenstates and zero, when the
projected wavefunctions perfectly represent the PW states. Unlike the
procedure of Sanchez-Portal *et al.* [48], the
basis functions are not scaled in order to optimise . This
gives spilling parameters in the region of which are
believed to be adequate for the purposes of this work.

The density operator may be defined,

where are the occupancies of the PW states, are the projected eigenstates, , and are the duals of these states. From this, the density matrix for the atomic basis set may be calculated as follows:

may be calculated in a time proportional to the cube of the system size, the same order of scaling as the original PW calculations, but the total time is smaller as there is no need to carry out iterations to achieve self-consistency.

The density matrix and the overlap matrix are sufficient to perform population analysis of the
electronic distribution. In Mulliken analysis [43] the
charge associated with a given atom *A* is given by

and the overlap population between two atoms *A* and *B* is

In Löwdin analysis [44] these quantities are given by

and

In Equations () and () the matrix is calculated as a Taylor expansion of where .

Details of the implementation of these methods may be found in Appendix .

Wed Sep 24 12:24:18 BST 1997